CN109952330A - Polyurethane-vinyl hybrid polymer object, its preparation method and their purposes - Google Patents
Polyurethane-vinyl hybrid polymer object, its preparation method and their purposes Download PDFInfo
- Publication number
- CN109952330A CN109952330A CN201780069526.7A CN201780069526A CN109952330A CN 109952330 A CN109952330 A CN 109952330A CN 201780069526 A CN201780069526 A CN 201780069526A CN 109952330 A CN109952330 A CN 109952330A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- alkyl
- group
- vinyl
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 122
- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 10
- -1 vinyl compound Chemical class 0.000 claims abstract description 96
- 239000004814 polyurethane Substances 0.000 claims abstract description 75
- 239000000853 adhesive Substances 0.000 claims abstract description 73
- 230000001070 adhesive effect Effects 0.000 claims abstract description 73
- 229920002635 polyurethane Polymers 0.000 claims abstract description 73
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 60
- XJDDLMJULQGRLU-UHFFFAOYSA-N 1,3-dioxane-4,6-dione Chemical compound O=C1CC(=O)OCO1 XJDDLMJULQGRLU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001450 anions Chemical class 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000004821 Contact adhesive Substances 0.000 claims abstract description 5
- 239000002390 adhesive tape Substances 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 73
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 39
- 125000000129 anionic group Chemical group 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 125000000623 heterocyclic group Chemical group 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 125000005647 linker group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920006254 polymer film Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 10
- 125000004423 acyloxy group Chemical group 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004414 alkyl thio group Chemical group 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012675 alcoholic extract Substances 0.000 claims description 6
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 6
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000010422 painting Methods 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000006870 function Effects 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 44
- 239000002585 base Substances 0.000 description 39
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 27
- 239000012948 isocyanate Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 150000002513 isocyanates Chemical class 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 18
- 239000010408 film Substances 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000002596 lactones Chemical class 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 210000004379 membrane Anatomy 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000007761 roller coating Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000005025 cast polypropylene Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 210000004400 mucous membrane Anatomy 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000005026 oriented polypropylene Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical group O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F22/14—Esters having no free carboxylic acid groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
Abstract
Describe polyurethane-vinyl hybrid polymer object, its preparation method and their purposes.Hybrid polymer object is made of anion polyurethane and polymerizable vinyl compound, and wherein polymerizable vinyl compound is selected from methylene malonate, methylene 'beta '-ketoester and methylene beta-diketon.The hybrid polymer object can be used as the adhesive in sqtructural adhesive, the adhesive in pressure-sensitive adhesive, the adhesive in laminated adhesive, the adhesive in contact adhesive, the adhesive in ink, the adhesive in paint, the adhesive in coating, the adhesive for fiber bonding, the adhesive in the adhesive or high cohesion adhesive tape for particle bonding.
Description
The present invention relates to polyurethane-vinyl hybrid polymer object, its preparation method and their purposes.Hybrid polymer object by yin from
Sub- polyurethane and polymerizable vinyl compound are made, and wherein polymerizable vinyl compound is selected from methylene malonate, Asia
Methyl 'beta '-ketoester and methylene beta-diketon.The hybrid polymer object can be used as adhesive in sqtructural adhesive, in pressure-sensitive adhesive
The adhesive, adhesive in laminated adhesive, the adhesive in contact adhesive, the adhesive in ink, viscous in paint
Adhesive in mixture, coating, the adhesive for fiber bonding, in adhesive or high cohesion adhesive tape for particle bonding
Adhesive.
Adhesive and adhesive are typically based on bi-component adhesive polymer objects system, which usually requires crosslinking agent to obtain
Enough adhesive strengths, chemical resistance or thermal stability.Particularly, compared with organic solvent based adhesive, water based pressure sensitive gluing
Agent usually has lower cohesive strength.Particularly, for the water-borne pressure sensitive adhesive stick (PSA) of high adhesive tape in adhesion strength/interior
The performance of solvent base PSA is generally unable to reach in terms of poly- dynamic balance.Although cohesive force can be improved by being crosslinked, this usually with it is viscous
It is related to put forth effort undesirable significant decrease.
Match preparing adhesive usually using isocyanate crosslinking and polyol component.These systems can be used as it is solvent-free and
Anhydrous 100% system is used as organic solvent based adhesive solution or as water base aqueous polymer dispersions.Disadvantage
It is that these preparations have the relatively low working time (referred to as working life), and since reactive isocyanate crosslinking agent may be
Healthy aspect is harmful.Accordingly, it is desirable to provide alternative adhesive and adhesive without isocyanates.Therefore, it is intended that mentioning
For the alternative cross-linked polymer without isocyanates, especially suitable for water base viscous with good adherence power/cohesion dynamic balance
Mixture or water accack.
WO2013/149168, which is described, in embodiment to be prepared using relatively great amount of adhesive laminated adhesive
Laminated product, the laminated adhesive include methylene malonate, methylene 'beta '-ketoester or methylene beta-diketon.
WO2013/149165 describes the polymerization reaction for causing methylene malonate He other polymerisable compounds
Activation method, such as activated by anionic mechanism, wherein polymerization activator is carried on polymerizable with disactivation bonding state
In composition.
WO2013/059473 describes polyfunctional monomer, and it includes multifunctional methylene malonates and methylene β -one
Ester monomer.
WO 2016/040012 is described carries out anionic polymerisation 1 in water in the presence of nonionic emulsifier and alkali,
The method of 1- disubstituted olefin (such as methylene malonate).
The composite membrane for flexible package is described application No. is the patent application that do not announce in advance of EP16161811.1
Laminate, wherein laminated adhesive include polymerizable vinyl compound, selected from methylene malonate, methylene 'beta '-ketoester and
Methylene beta-diketon.Aqueous anionic polyurethane dispersion can be used as priming coat, wherein the anionic group of polyurethane with can gather
The molar ratio for closing the vinyl of vinyl compound is 1:10 to 1:100 ten thousand.
WO 2006/087317 describes the dispersions of polyurethanes for composite membrane lamination.
The object of the present invention is to provide the alternative cross-linked polymer without isocyanates, it is suitable for coating and adhesive
Adhesive especially has good adherence power/cohesion dynamic balance water-based adhesive or water accack.
It has been found that the vinyl compound selected from methylene malonate, methylene 'beta '-ketoester and methylene beta-diketon exists
Anionic polymerisation occurs in the discrete particles of aqueous polyurethane dispersion, the excellent polyurethane-vinyl of forming properties is mixed
Heteropolymer.For example, the pressure-sensitive adhesive obtained by aqueous polyurethane dispersion and methylene malonate is in tape applications
High cohesion and high fissility are shown to steel.
It has been found that the purpose of the present invention can be by by least one anion polyurethane and at least one polymerizable vinyl
Polyurethane-vinyl hybrid polymer object made of compound realizes that wherein polymerizable vinyl compound is selected from methylene the third two
Acid esters, methylene 'beta '-ketoester and methylene beta-diketon；
Also, wherein
A) polyurethane-vinyl hybrid polymer object by first with aqueous anionic polyurethane dispersion coat substrate and with
It is applied and is formed outside with polymerizable vinyl compound afterwards, wherein the anionic group of polyurethane and polymerizable vinyl chemical combination
The ratio of the vinyl of object is less than or equal to 50:1 greater than 1:9, preferably at least 1:1 or greater than 1:1；
Or
B) wherein polyurethane-vinyl hybrid polymer object is formed in aqueous dispersion.
Preferably, polyurethane-vinyl hybrid polymer object is made of methylene malonate.
Hybrid polymer object is at least two other structural units of different polymeric types comprising being connected to each other on a molecular scale
Polymeric material.
Adhesive, the pressure sensitive adhesive being used as in sqtructural adhesive the present invention also provides polyurethane-vinyl hybrid polymer object
The adhesive in adhesive, laminated adhesive in stick, the adhesive in contact adhesive, the adhesive in ink, paint
In adhesive, the adhesive in coating, for fiber bonding adhesive, for particle bonding adhesive or high cohesion glue
The purposes of adhesive in adhesive tape.Contact adhesive is the adhesive that two surfaces to be bonded are applied.
The present invention also provides it is a kind of formed polyurethane-vinyl hybrid polymer object method,
Wherein, at least one anion polyurethane is reacted at least one polymerizable vinyl compound, described polymerizable
Vinyl compound is selected from methylene malonate, methylene 'beta '-ketoester and methylene beta-diketon,
It wherein reacts and carries out in liquid medium, to be formed comprising at least one polyurethane-vinyl hybrid polymer object
Single-component composition；
Or in which by the first liquid composition comprising at least one anion polyurethane and comprising at least one polymerizable
The second liquid composition of vinyl compound mixes, and is subsequently applied on substrate, and polyurethane-vinyl hybrid polymer object
Formation at least partly occur after being administered on substrate；
Or in which polyurethane-vinyl hybrid polymer object is by coating substrate at least one anion polyurethane first
And then applied first coating at least one polymerizable vinyl compound outside and formed, wherein the anionic group of polyurethane with
The molar ratio of the vinyl of polymerizable vinyl compound is greater than 1:9, preferably greater than 1:1.
Glass transition temperature (Tg) passes through differential scanning calorimetry (ASTM D 3418-08, neutral temperature, the rate of heat addition
20 DEG C/min) measurement.
Unless otherwise stated, room temperature is 20 DEG C.
Polymerizable vinyl compound has one, two or more methylene=CH2。
Methylene malonate is comprising at least one (such as one, two or more)~O-C (O)-C (C=
CH2)-C (O)-O~group compound.
Methylene 'beta '-ketoester is comprising at least one (such as one, two or more)~C (O)-C (C=CH2)-C
(O)-O~group compound.
Methylene beta-diketon is comprising at least one (such as one, two or more)~C (O)-C (C=CH2)-C
(O)~group compound.
Preferred methylene malonate is the compound of following formula
R1- O-C (O)-C (C=CH2)-C(O)-O-R2
Preferred methylene 'beta '-ketoester is the compound of following formula
R1- C (O)-C (C=CH2)-C(O)-O-R2
Preferred methylene beta-diketon is the compound of following formula
R1- C (O)-C (C=CH2)-C(O)-R2
Wherein R1、R2It is each independently C1-C15 alkyl, C2-C15 alkenyl, halogenated-(C1-C15 alkyl), C3-C6 cycloalkanes
Base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl
Base or heteroaryl-(C1-C15 alkyl) or alkoxy-(C1-C15 alkyl), are respectively optionally replaced by following group: C1-
C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-
C15 alkyl), it is aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl, nitro, folded
Nitrogen base, cyano, acyloxy, carboxyl, ester or sulfonyl；
Or in which R1And R2Atom in connection is formed together 5-7 circle heterocyclic ring, and the heterocycle is optionally by following base
Group replaces: C1-C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, miscellaneous
Ring group-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl
Base, nitro, azido, acyloxy, carboxyl, ester or sulfonyl.
Polymerizable vinyl compound can be simple function, i.e., only have mono-vinyl or they can be there are two tools
The above vinyl it is polyfunctional.Preferred multifunctional polymerizable vinyl compound is following formula:
Wherein R1、R2It is each independently C1-C15 alkyl, C2-C15 alkenyl, halogenated-(C1-C15 alkyl), C3-C6 cycloalkanes
Base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl
Base or heteroaryl-(C1-C15 alkyl) or alkoxy-(C1-15 alkyl), are respectively optionally replaced by following group: C1-
C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle (C1-C15
Alkyl), aryl, aryl (C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl, nitro, nitrine
Base, cyano, acyloxy, carboxyl, ester or sulfonyl；
Or in which R1And R2Atom in connection is formed together 5-7 circle heterocyclic ring, and the heterocycle is optionally below
Group replace: C1-C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle,
Heterocycle-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group,
Hydroxyl, nitro, azido, acyloxy, carboxyl, ester or sulfonyl；
[A]-representative-(CRARB)n-、-(CRARB)n- O (C=O)-(CH2)1-15(C=O) O- (CRARB)n-、-(CH2)n-
[CY]-(CH2)n, polybutadiene-base linking group, polyethylene glycol linking group, polyethers linking group, polyurethane linking group, ring
Oxygen linking group, polyacrylic acid linking group or polycarbonate linking group；
RAOr RBIt is each independently H, C1-C15Alkyl, C2-C15Alkenyl, the part being expressed from the next:
Wherein L be linking group selected from the following: alkylidene, alkenylene, halogeno alkylen, cycloalkylidene, cycloalkylidene,
Sub- heterocycle, heterocycloalkylene, aryl-alkylidene, inferior heteroaryl or heteroaryl-(alkylidene) or alkoxy-(alkylene
Base), it is optionally respectively branching, and it is respectively optionally replaced by following group: alkyl, halogenated alkyl, ring
Alkyl, halogenated cycloalkyl, heterocycle, heterocycle-(alkyl), aryl, aryl-(alkyl), heteroaryl, C1-C15Alkoxy, C1-
C15Alkylthio group, hydroxyl, nitro, azido, cyano, acyloxy, carboxyl, ester, the group are optionally respectively branching；
R3Independently selected from above-mentioned R2Defined in group；
[CY] indicates alkyl, alkenyl, halogenated alkyl, naphthenic base, halogenated cycloalkyl, heterocycle, heterocycle-(alkyl), virtue
Base-(alkyl), heteroaryl or heteroaryl-(alkyl) or alkoxy-(alkyl)；
The integer that n is 1 to 25；
The integer that m is 1 to 25, preferably 2 to 25 integer；
And Q respectively representative-O- or direct key.
Preferred polyurethane-vinyl hybrid polymer object is that wherein polymerizable vinyl compound is selected from those of the formula
R1- O-C (O)-C (C=CH2)-C(O)-O-R2
Wherein R1、R2It is each independently C1-C10 alkyl, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptan
Base, octyl etc., and wherein alkyl can be straight chain, branching or cricoid；
Or in which polymerizable vinyl compound is selected from the compound of following formula:
Wherein R1、R2It is each independently C1-C10 alkyl, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptan
Base, octyl etc., and wherein alkyl can be straight chain, branching or cricoid；
A is selected from C1-C10 alkylidene and-X-Ph-Y-, and wherein X and Y is each independently C1-C10 alkylidene, most preferably sub-
Methyl.C1-C10 alkylidene can be methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc..
The method for preparing methylene malonate is documented in WO 2014/110388, WO2012/054616 and WO 2012/
In 054633.The method for preparing methylene beta-diketon is documented in WO 2013/059479.The method for preparing methylene 'beta '-ketoester
It is documented in WO 2013/066629.The method for preparing polyfunctional vinyl compound is documented in WO 2013/059473.
The amount of the anionic group of polyurethane is preferably 50mmol/kg to 500mmol or 50mmol/kg to 450mmol/
Kg, based on siccative.It is preferred that the anionic group of polyurethane is selected from carboxylate group, sulfonate group and phosphate groups.Most
Preferably carboxylate group, especially sodium or potassium are as ion balance.
Anion polyurethane is the polyurethane comprising anionic group.Anionic group can be suspended on polyurethane skeleton
On or they can be the end on polymer chain terminal.Preferred anionic group hangs on the anion on polyurethane skeleton
Polyurethane.
Anion polyurethane includes the monomer with anionic group as structural constituent.Anionic group is specifically for sulfonic acid
Foundation group, carboxylate group and phosphate groups, they are the form of salt, such as their alkali metal salt or their ammonium salt.
Other anionic groups for the purpose of the present invention are that can be converted to above-mentioned ion by simple neutralization reaction or hydrolysis
The potential anionic group of hydrophilic radical, therefore example has carboxylic acid group.Ion monomer and potential ion monomer are recorded in detail
In such as UllmannsDer technischen Chemie [Liv Ullmann industrial chemistry encyclopaedia],
In 4th edition page 311 page -313 of volume 19 and such as DE-A 1 495 745.
Anion polyurethane is preferably made of following components: a) polyisocyanates, preferably at least a kind of diisocyanate, b)
Polyalcohol, preferably at least a kind of polyester-diol and/or at least one polyetherdiol and c) its optionally with reactive group
His simple function or polyfunctional compound, the reactive group is for example selected from alcoholic extract hydroxyl group, primary amino group, secondary amino group and isocyanates
Base, wherein at least one structural constituent have one or more anionic groups.
The example of suitable diisocyanate is Formula X (NCO)2Those of, wherein X is the rouge with 4 to 15 carbon atoms
Race's alkyl, the alicyclic or aromatic hydrocarbyl with 6 to 15 carbon atoms or the araliphatic hydrocarbon radical with 7 to 15 carbon atoms.This
The example of a little diisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, ten dimethylene diisocyanates
Ester, hexamethylene -1,4- diisocyanate, 3,5,5- trimethyl -5- isocyanatomethyl cyclohexane -1- isocyanates (IPDI),
Bis- (the 4- NSC 87419 base) propane of 2,2-, trimethylhexane diisocyanate, 1,4- phenylene diisocyanate, 2,4- toluene two
Isocyanates, 2,6- toluene di-isocyanate(TDI), 4,4'- diisocyanate root close diphenyl methane, 2,4'- diisocyanate root closes hexichol
Methylmethane, paraxylene diisocyanate, tetramethylxylene diisocyanate (TMXDI), bis- (4- NSC 87419 bases)
The isomers (HMDI) of methane, such as trans/trans isomers, cis-/cis-isomer and cis/trans isomers, and
The mixture being made of these compounds.These diisocyanate are commercially available.The especially important of these isocyanates is mixed
The mixture for closing the corresponding constitutional isomer that object is toluene di-isocyanate(TDI) and diisocyanate root conjunction diphenyl methane, is especially closed
Suitable is the mixing made of the 2,4 toluene diisocyanate of 80 moles of % and the 2,6- toluene di-isocyanate(TDI) of 20 moles of %
Object.Aromatic isocyanate (such as 2,4 toluene diisocyanate and/or 2,6- toluene di-isocyanate(TDI)) with aliphatic series or it is alicyclic different
The mixture of cyanate (such as hexamethylene diisocyanate or IPDI) is also particularly advantageous, preferred aliphatic series and aromatics isocyanide
The mixing ratio of acid esters is 1:9 to 9:1, especially 1:4 to 4:1.
The structure of polyurethane, which also can be used, also has other blocked isocyanate bases not only with free isocyanate groups group
The isocyanates of group's (such as uretdion), as the polyisocyanate compound other than above compound.
Preferably, every kind in polyurethane is by least 40 weight %, particularly preferably at least 60 weight % and very especially excellent
The choosing at least diisocyanate of 80 weight %, polyetherdiol and/or polyester-diol are constituted.Preferably, polyurethane includes based on poly-
The amount of urethane meter is greater than 10 weight %, especially preferred more than 30 weight %, particularly to be greater than 40 weight % or be greater than 50 weights
Measure % and the very particularly preferably polyester-diol greater than 60 weight % or polyetherdiol or its mixture.
Workable polyester-diol is mainly the glycol of relatively high molecular weight, and molal weight is 500 to 5000g/mol,
Preferably from about 1000 to 3000g/mol.The molal weight of polyetherdiol is preferably 240 to 5000g/mol.This is mumber average molar mass
Mn.Mn is determined by determining end group number (OH number).
Polyester-diol is known in such as UllmannsDer technischen Chemie [Wu Er
Graceful industrial chemistry encyclopaedia], the 4th edition, volume 19, page 62 to 65.It is preferable to use reacted by dihydric alcohol with dicarboxylic acids
Polyester-diol obtained.In addition to free carboxy acid, it is possible to use the polycarboxylate of corresponding multi-carboxy anhydride or corresponding lower alcohol or
These mixture prepares polyester polyol.Polycarboxylic acid can be aliphatic, alicyclic, araliphatic, aromatics or heterocyclic, and such as
Fruit is suitable, can have unsaturated state and/or substitution, such as halogen atom replaces.The example that they can be mentioned that are as follows: suberic acid, nonyl
Diacid, phthalic acid, M-phthalic acid, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, four
Chloro-phthalic anhydride, Nadic anhydride, dimer (fatty acid) yl.Preferred formula HOOC- (CH2)y- COOH's
Dicarboxylic acids, wherein y is 1 to 20 number, preferably 2 to 20 even number, and example has succinic acid, adipic acid, decanedioic acid and dodecane two
Carboxylic acid.
Can be used for preparing the dihydric alcohol of polyester-diol example have ethylene glycol, propane -1,2- glycol, propane -1,3- glycol,
Butane -1,3- glycol, butylene-1,4-diol, butine -1,4- glycol, pentane -1,5- glycol, neopentyl glycol, bis- (methylol) rings
Bis- (methylol) hexamethylenes of hexane such as 1,4-, 2- methylpropane -1,3- glycol, methyl pentanediol and diethylene glycol, three second two
Alcohol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polytetramethylene glycol.Preferred formula is HO- (CH2)x-
The alcohol of OH, wherein x is 1 to 20 number, preferably 2 to 20 even number.The example of these materials have ethylene glycol, butane -1,4- glycol,
Hexane -1,6- glycol, the pure and mild dodecane -1,12- glycol of octane -1,8- two.Further preferred neopentyl glycol.
, if appropriate, can also be with polycarbonate glycol be used other than polyester-diol or polyetherdiol, it can be such as
It is reacted by phosgene with the low-molecular-weight alcohol that the excessive structural constituent as polyester polyol refers to obtain.If appropriate,
The polyester-diol based on lactone can also be used, they are the homopolymer or copolymer of lactone, preferably originate from lactone and add to conjunction
On suitable bifunctional starting molecule and with terminal hydroxyl product.The lactone that can be used preferably derives from general formula HO-
(CH2)zThose of compound of-COOH, wherein z is 1 to 20 number, and the hydrogen atom of methylene units can also be by C1-C4
Alkyl replaces.Example is 6-caprolactone, beta-propiolactone, gamma-butyrolacton and/or methyl-epsilon-caprolactone and their mixing
Object.The example of suitable starter components is the low molecular weight diol that the above-mentioned structural constituent as polyester polyol refers to.
Particularly preferably corresponding 6-caprolactone polymer.Lower polyester diols or polyetherdiol also are used as preparing rising for lactone polymer
Beginning agent.In addition to lactone polymer, the corresponding chemical equivalence condensation polymer using the hydroxycarboxylic acid for corresponding to lactone can also be substituted.
Polyetherdiol especially can be for example, by BF3In the presence of ethylene oxide, propylene oxide, epoxy butane, tetrahydro furan
Mutter, it is prepared by the homopolymerization of styrene oxide or epoxychloropropane, or by by these compounds --- if applicable to mix
Close object or continuous mode --- it adds in the starter components with hydrogen atoms, the example of the starter components
For alcohol or amine, for example, bis- (4- hydroxy phenyl) propane of water, ethylene glycol, propane -1,2- glycol, propane -1,3- glycol, 2,2- or
Aniline.The polytetrahydrofuran that particularly preferred propylene oxide and number-average molecular weight are 240 to 5000, particularly 500 to 4500.It is excellent
Select the polyetherdiol by constituting less than 20 weight % ethylene oxide.
Can also preferably have 2 terminal hydroxyls, such as α, ω-dihydroxy with using poly- alkene as monomer (c1)
Base polybutadiene, α, alpha, omega-dihydroxy polymethacrylates or α, alpha, omega-dihydroxy polyacrylate.These compounds are known in
Such as in EP-A 622 378.Other suitable polyalcohols are polyacetals, polysiloxanes and alkyd resin.
Polyetherdiol is preferably selected from polytetrahydrofuran and polypropylene oxide.Polyester-diol preferably is selected from dihydric alcohol and dicarboxylic acids
Reaction product and lactone-based polyester diol.
It if desired, when glycol used not only includes polyester-diol and polyetherdiol, but also include rubbing of being different from
When the low molecular weight monomers glycol that your quality is about 60 to 500g/mol, preferably 62 to 200g/mol, the hardness and bullet of polyurethane
Property modulus can increase.The low molecular weight monomers glycol used especially prepares short alkanediol mentioned by polyester polyol
Structural constituent, herein preferably with 2 to 12 carbon atoms and with the unbranched glycol of even number of carbon atoms, and preferably penta
The pure and mild neopentyl glycol of alkane -1,5- two.Example have ethylene glycol, propane -1,2- glycol, propane -1,3- glycol, butane -1,3- glycol,
Butylene-1,4-diol, butine -1,4- glycol, pentane -1,5- glycol, neopentyl glycol, bis- (methylol) hexamethylenes such as 1,4- are bis-
(methylol) hexamethylene, 2- methylpropane -1,3- glycol and methyl pentanediol, other workable compounds have diethylene glycol,
Triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polytetramethylene glycol.Preferred formula is HO-
(CH2)xThe alcohol of-OH, wherein x is 1 to 20 number, preferably 2 to 20 even number.An example here is ethylene glycol, butane -1,4- glycol,
Hexane -1,6- glycol, the pure and mild dodecane -1,12- glycol of octane -1,8- two.Further preferred neopentyl glycol.Based on all glycol
Total amount meter, the ratio of polyester-diol and polyetherdiol is preferably 10 to 100 moles of %.And the total amount based on all glycol
Meter, the ratio of low molecular weight monomers glycol is preferably 0 to 90 mole of %.Particularly preferred polymer diol and the ratio of monomeric diol are
0.1:1 to 5:1, especially 0.2:1 are to 2:1.
In order to improve the water dispersible of polyurethane, polyurethane also may include as structural constituent at least one isocyanide
Acid esters group has at least one to the reactive group of isocyanate groups and also at least one hydrophily base
The monomer of group or a group that can be converted to hydrophilic radical.Monomer of the hydrophilic radical than being used as polymer backbone conformation
Functional group more slowly reacts with isocyanates.Based on the total amount of all structural constituents of polyurethane, with hydrophilic radical
The ratio of component usually judges in this way: the total weight based on all monomers, the mole of hydrophilic radical be 30 to
1000mmol/kg, preferably 50 to 500mmol/kg, particularly preferred 80 to 300mmol/kg.Hydrophilic radical can be nonionic
Or preferred ion hydrophilic radical.Workable nonionic hydrophilic moieties are specifically for preferably by 5 to 100, preferably 10 to 80
The polyglycol ether of a ethylene oxide repeating units composition.The content of polyalkylene oxide unit is usually 0 to 10 weight %, preferably
0 to 6 weight %, based on the total amount of all monomers.The preferred monomer with nonionic hydrophilic moieties is at least 20
The reaction product of the polyethylene oxide glycol of weight % ethylene oxide, polyethylene oxide monohydric alcohol and polyethylene glycol and two different
The reaction product of cyanate, wherein they have the polyethylene group of end etherificate.Patent specification US-A 3,905,929
Such diisocyanate and preparation method thereof is listed with US-A 3,920,598.
Anion polyurethane can be made of the monomer with anionic group and/or potential anionic group, such as with
At least one alcoholic extract hydroxyl group or aliphatic, alicyclic, araliphatic or aromatic carboxylic acid or sulfonic acid at least one primary or secondary amino.It is excellent
Dihydroxyalkyl carboxylic acid is selected, especially there is those of 3 to 10 carbon atoms, be also documented in US-A 3,412,054.It is especially excellent
The compound of gating formula (c1)
Wherein R1And R2It is C1-C4Alkane diyl unit and R3It is C1-C4Alkyl unit, especially dihydromethyl propionic acid
(DMPA).Other suitable (potential) anionic monomer compounds are corresponding dihydroxy sulfonic acid and dihydroxy phosphonic acids, such as 2,
3- dihydroxypropane phosphonic acids.Other suitable anionic monomer compounds are the molal weights at least two carboxylate groups
For 500 to 10000g/mol dihydroxy compounds and be disclosed in DE-A 39 11 827.They can pass through dihydroxy chemical combination
Object and tetracarboxylic dianhydride (such as pyromellitic acid dianhydride or pentamethylene tetracarboxylic dianhydride) are in sudden reaction with 2:1 to 1.05:1's
Molar ratio reaction obtains.Specially suitable dihydroxy compounds is the monomer listed as chain extender and above-mentioned glycol.
Particularly preferred anion structure component has carboxyl.Carboxyl can have at least one alcoholic extract hydroxyl group by above-mentioned
Or aliphatic, alicyclic, araliphatic at least one primary or secondary amino or aromatic carboxylic acid are introduced into polyurethane.It is preferred that dihydroxy
Alkyl carboxylic acid especially has 3 to 10 carbon atoms, especially dihydromethyl propionic acid.One kind being particularly preferred for anion
The structural constituent of polyurethane is bis- (methylol) propionic acid (dihydromethyl propionic acid, DMPA) of 2,2-.
It is workable have be amino carboxylic acid, example to other anion structure components of the reactive amino of isocyanates
Such as two primary diamines of aliphatic series and α, beta-unsaturated carboxylic acid or sulfonic acid mentioned in lysine or Beta-alanine or DE-A 20 34 479
Addition product.These compounds such as meeting formula (c2)
H2N-R4-NH-R5-X (c2)
Wherein R4And R5It is C independently of one another1-C6Alkane diyl unit, preferably ethylidene, X are COOH or SO3H.It is especially excellent
The compound for selecting formula (c2) is N- (2- amino-ethyl) -2- aminoethane carboxylic acid and N- (2- amino-ethyl) -2- amino second sulphur
Sour and corresponding alkali metal salt, particularly preferred Na is as ion balance herein.Further particularly preferably above-mentioned aliphatic di-primary amine with
The addition product of 2- acrylamide-2-methylpro panesulfonic acid, such as those of described in DE-B 1 954 090.
If using have potential ionic group monomer, can before or during isocyanates-sudden reaction with
And ionic species preferably is converted them into later, because ion monomer is usually only very slightly soluble in reaction mixture.Neutralizer
Example is ammonia, NaOH, triethanolamine (TEA), tri-isopropyl amine (TIPA) or morpholine, or derivatives thereof.It is particularly preferred that with alkali gold
Belong to ion or ammonium ion as ion balance, sulfonate radical or carboxylate group are become to the form of its salt.
In addition, polyfunctional monomer can be used for crosslinking or the chain extension of polyurethane.These are usually not only binary non-phenolic alcohol, tool
There are the amine of 2 or more uncles and/or secondary amino group or not only with one or more alcoholic extract hydroxyl groups but also with one or more
The compound of a uncle and/or secondary amino group.It can be used for adjusting the alcohol with the degree of functionality higher than 2 of specific branching or crosslinking degree
Example is trimethylolpropane, glycerol or sugar.Polyamines and list with 2 or more uncles and/or secondary amino group also can be used
Alcohol, wherein they are other than with hydroxyl, and also with to the reactive other groups of isocyanates, example is with one
Or the monohydric alcohol of multiple uncles and/or secondary amino group, such as monoethanolamine.Polyurethane preferably comprises 1 to 30 mole of %, particularly preferred 4
To the polyamines at least two pairs of reactive amino of isocyanates of 25 moles of %, the total amount based on all structural constituents
Meter.For identical purpose, it is possible to use degree of functionality is greater than 2 isocyanates.The example of commercial compound is isocyanuric acid ester
Or the biuret of hexamethylene diisocyanate.
The monofunctional monomer optionally employed is monoisocyanates, monohydric alcohol, primary monoamine and single secondary amine.Always rubbing based on monomer
That meter, their ratio are usually at most 10 moles of %.These monofunctional compounds usually have other functional groups, such as alkene
Hydrocarbyl group or carbonyl, and allow they or crosslinking for being introduced in polyurethane or carry out similar anti-of other polymers
The functional group answered.Can be used for ester that this monomer is isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (TMI) and acrylic acid or
The ester of methacrylic acid, such as hydroxy-ethyl acrylate or hydroxyethyl methacrylate.
The arithmetic of reactive functional groups quantity in ratio and selection per molecule by selecting the monomer that can be reacted with each other
Average value is known in art of polyurethane chemistry come the method for adjusting the molecular weight of polyurethane.Generally select component and it
Respective mole so that ratio A:B be 0.5:1 to 2:1, preferably 0.8:1 to 1.5:1, particularly preferably 0.9:1 are extremely
1.2:1, wherein
A is the mole of isocyanate groups,
B is the summation of the mole of hydroxyl and the mole for the functional group that can be reacted with isocyanates in addition reaction.
Very particularly preferably ratio A:B is as close possible to 1:1.It is 1.5 to 2.5, preferably 1.9 that monomer, which usually has average value,
Isocyanate groups and the functional group that can be reacted in addition reaction with isocyanates accordingly to 2.1, particularly preferred 2.0.
The sudden reaction of the structural constituent of polyurethane is used to prepare preferably at up to 180 DEG C, preferably up to 150 DEG C
It is carried out under atmospheric pressure or self-generated pressure under reaction temperature.The preparation of polyurethane and the preparation of aqueous polyurethane dispersion are for this
It is known for the technical staff of field.
Anion polyurethane is preferably made of following components:
A) diisocyanate,
B) polyester-diol of the molal weight greater than 500 to 5000g/mol and/or molal weight are 240 to 5000g/mol
Polyetherdiol,
C) with the glycol of carboxylic acid group, and
D) optionally other simple functions or polyfunctional compound are different from a)-c) and have and be selected from alcoholic extract hydroxyl group, primaquine
The reactive group of base, secondary amino group and isocyanate group.
Polyurethane preferably uses the form of water-borne dispersions, and is preferably used in and vinyl compound in this form
In reaction.
Polyurethane-vinyl hybrid polymer object of the invention preferably is contained in liquid composition, for example, organic solvent or
Most preferably it is included in water-borne dispersions in a dispersed form.
Polyurethane-vinyl hybrid polymer object of the invention is preferably made of such anion polyurethane, polymerizable
The glass transition temperature of polymerization of vinyl compound foregoing description anion polyurethane is lower than 0 DEG C, preferably shorter than -10 DEG C.
In one embodiment of the invention, polyurethane-vinyl hybrid polymer object is such polymer: wherein being gathered
The ratio of the vinyl of the anionic group and polymerizable vinyl compound of urethane is greater than 1:1, and polymerizable vinyl
Conjunction object is at least one multifunctional methylene malonate with two or more methylene malonate groups.
The invention further relates to high cohesion pressure-sensitive adhesives, can be prepared by using flexible polyurethane, preferably in aqueous poly-
The form of urethane dispersion.Flexible polyurethane is the polyurethane that glass transition temperature is lower than -10 DEG C.
High cohesion pressure-sensitive adhesive (as defined herein) is such pressure-sensitive adhesive, and it is big to be defined as peel strength
In 10N/25mm, room temperature shear strength is greater than 60min, as be shown in the examples to measure.
The invention further relates at room temperature be hemicrystalline polyurethane-vinyl hybrid polymer object, by it is amorphous yin from
Sub- polyurethane is reacted at least one polymerizable vinyl compound to be made；The polymerizable vinyl compound is selected from methylene
Malonate, methylene 'beta '-ketoester and methylene beta-diketon, preferably methylene malonate, especially diethyl methylene the third two
Acid esters.
Amorphous polyurethane can be fixed by using amorphous polymer polyols preparation, such as amorphous polyether polyol, nothing
Shape polycarbonate polyol, amorphous poly- alkene or amorphous polyester polyalcohol.Preferably amorphous polyether polyol is
Polypropylene glycol and poly- THF.Preferred amorphous polyester polyalcohol be aromatics/aliphatic series mix diacid polyesterols or straight chain diacid and
The polyesterols of branched glycol.
Semicrystalline polyurethane-vinyl hybrid polymer object is be especially suitable for laminated adhesive.
The invention further relates to be amorphous at room temperature and by semicrystalline polyurethane and at least one polymerizable ethylene
Based compound is crosslinked and manufactured polyurethane-vinyl hybrid polymer object, and the polymerizable vinyl compound is selected from methylene
Malonate, methylene 'beta '-ketoester and methylene beta-diketon, preferably methylene malonate.
Semicrystalline polyurethane can be tied for example by using the rule for being greater than 50 weight % (based on all macromolecular diols)
Polyesterols (such as polyester of alkylidene diacid (such as adipic acid) and linear diols (such as 1,6-HD or 1,4- butanediol) of structure
Alcohol) or polycaprolactone prepare.
Semi-crystalline polymer is the polymer of crystallinity preferably 10 to 80% at room temperature.Amorphous polymer is in room temperature
Lower crystallinity is preferably smaller than 10% polymer.Crystalline polymer is the polymer that crystallinity is preferably greater than 80% at room temperature.
Crystallinity can be measured by differential scanning calorimetry.
Polyurethane-vinyl hybrid polymer object can be used in the form of single-component composition, optionally include conventional add
Add agent.Preferred single-component composition is water-borne dispersions form, contains at least one polyurethane-vinyl being dispersed in water
Hybrid polymer object.Discrete particles include the polyvinyl of polyurethane and anionic polymerisation, the polymer including grafting simultaneously
Structure uses the polyurethane of vinyl polymer graft.These dispersions are by the property of anion polyurethane and polyvinyl
Matter is incorporated in single discrete particles.
Polymerization can be realized under room temperature (25 DEG C or lower), simply by polymerizable vinyl compound is added to water
In property dispersions of polyurethanes and stir progress.It can accelerate by temperature is increased to room temperature or more and/or complete to polymerize.
Emulsifier can be added with stabilized aqueous polyurethane-vinyl hybrid polymer object dispersion.Preferably, using not causing
Or slow down the emulsifier of the anionic polymerisation of polyvinyl.Preferred emulsifier is non-ionic.Cream is not added more preferably
Agent.
Polyurethane-vinyl hybrid polymer object can also be used in the form of two-component composition.It is used to form polyurethane-second
The two-component composition of alkenyl hybrid polymer object is such composition: wherein the first liquid composition include at least one yin from
Sub- polyurethane, second liquid composition include at least one selected from methylene malonate, methylene 'beta '-ketoester and methylene β-
The polymerizable vinyl compound of diketone.First and second compositions are respectively optionally including conventional additives.Preferred
One composition is the form of aqueous polyurethane dispersion, contains at least one anion polyurethane being dispersed in water.By two
It is applied on substrate at once after kind component mixing.Preferably, at least part of polyurethane-vinyl hybrid polymer object is being applied
It is formed after forming a film after on substrate and/or on substrate.
The example of optional additive includes wetting agent, thickener, protecting colloid, UV- absorbent, light stabilizer, kills livestock
Agent, defoaming agent, tackifier, antioxidant, matal deactivator, antistatic agent, reinforcing agent, packing material, antifoggant, propulsion
Agent, plasticizer, lubricant, emulsifier, colorant, pigment, rheology modifier, impact modifier, adhesion modifying agent, fluorescent brightening
Agent, fire retardant, dripping inhibitor, nucleating agent, protecting colloid, water, organic solvent, reactive diluent etc..
Polyurethane-vinyl hybrid polymer object can be used as the adhesive of such as coating or the adhesive of adhesive.Adhesive
Or coating composition or the preparation suitably prepared can be applied in be bonded or be applied for example, by modes such as cutter painting, blade coating, sprayings
On the substrate covered.Can be used typical paint-on technique, example be roller coating, reversed roller coating, intaglio plate roller coating, reversed intaglio plate roller coating,
Brushing, stick painting, spraying, air-brush coating, meniscus painting, curtain coating or dip-coating.After the solvent of dispersion or the evaporation of water short time (preferably
After 1 to 60 second), in the case where adhesive applications, then coated substrate can be contacted with the second substrate, for temperature
Such as 20 to 200 DEG C, preferably 20 to 100 DEG C, pressure is such as 0.1 to 3000kN/m2, preferably 0.2 to 10kN/m2。
Coating can be for example with 0.1 to 2000g/m2Amount application, preferably 1 to 200g/m2Amount.Coating layer thickness is preferably 0.1
μm to less than 2000 μm, such as 1 to 200 μm.In the case where containing the coating formulation of solvent (such as water or organic solvent), apply
Thickness degree is the thickness of dry coating after solvent evaporation.
It is preferred that using composition of the invention, more particularly isocyanate-free crosslinking agent without additional crosslinking agent.Suitably
The example of substrate includes polymer film, more particularly polyethylene (PE), oriented polypropylene (OPP), non-directional polypropylene (CPP),
Polyamide (PA), polyethylene terephthalate (PET), poly- acetic acid esters, PVC, glassine paper (are steamed with metal (such as with aluminium)
Gas -) coating polymer film (abbreviation metallized film) or metal foil, such as aluminium foil.The film and foil can be bonded to each other or
Bonded with different types of foil or film --- for example, polymer film and metal foil, polymer film different from each other etc..The foil
It can also be for example with off-set oil ink print with film.The thickness of base material film can be such as 5 to 100 μm, preferably 5 to 40 μm.
One embodiment of the invention is composite membrane, wherein the material of the first film is selected from OPP, CPP, PE, PET and PA,
The material of second film is selected from OPP, CPP, PE, PET, PA and metal foil.In one embodiment of the invention, the first film and/
Or second film metallize or print in the respective face for being coated with Inventive polymers dispersion.
It is not indispensable for being surface-treated before coating to film base material according to the present invention.However, if applying
The surface of modified film base material, then can get better result before covering.In such a case, it is possible at using typical surface
Reason, example is sided corona treatment, to enhance adhesion effect.Sided corona treatment or other surfaces processing proceed to coating composition and sufficiently moisten
Wet required degree.In general, every square metre of about 10 watts of sided corona treatment per minute is sufficient this purpose.As substitution or
Person is additional, and conventional primary coat or adhesive layer (tie are also used optionally between film base material and adhesive coating or precoated shet
coat).In addition, other additional functional layers can reside on composite membrane, example is barrier layer, printing layer, coloring layer or clear
Paint layer or protective layer.These functional layers can be located at outside, i.e., in the side of the film base material away from the side for being coated with adhesive；
Or it is internally positioned, between film base material and gluing oxidant layer.
The example of other suitable substrates includes hard substrate, such as metal, glass, plastics (such as acrylonitrile-butadiene-
Styrol copolymer (ABS), polyamide (PA), polystyrene (PS), polyvinyl chloride (PVC), polycarbonate (PC), rubber), wood
Material, particieboard, hardboard and polymer composites.The bonding or coating of these substrates can be at surface treatments such as plasma
It is carried out after reason or sided corona treatment, etching, flame treatment or primary coat application, but if using mixture according to the present invention, then
It is preferred that being completed without any processing.
Coating or adhesive solidify preferably lower than 100 DEG C at a temperature of, most preferably 15 to 30 DEG C or environment temperature.
Method of the invention is the method to form laminate, wherein
(1) at least one anion polyurethane (as described above) coated polymer film；
(2) coated polymer film is stored at least 1 day (preferably at ambient conditions)；
(3) apply coated polymer film outside at least one polymerizable vinyl compound, wherein polyurethane yin from
The molar ratio of the vinyl of subbase group and polymerizable vinyl compound is greater than 1:9, preferably greater than 1:1,
And wherein polymerizable vinyl compound is selected from methylene malonate, methylene 'beta '-ketoester and methylene β-two
Ketone；
And wherein polymerizable vinyl compound has at least two, preferably at least three to be selected from methylene malonate
The functional group of group, methylene 'beta '-ketoester group and methylene beta-diketon group；With
(4) polymer film by outer painting is laminated on substrate.Substrate can be one of above-mentioned substrate, preferably as described above separately
A kind of polymer film or hard substrate.Lamination can carry out under heating and boosting.Laminating temperature can be such as 20 to 200 DEG C,
It is preferred that 40 to 100 DEG C.Lamination pressure can be such as 100 to 3000kN/m2, preferably 300 to 2000kN/m2。
It is one advantage of the present invention that a variety of different substrates can be bonded or be coated, it is ensured that adhesive compound or coating
Composition is effectively bonded on various substrates and generates in bonded assemblies high-intensitive.
Particularly, the specific advantage of product of the present invention is as follows:
It realizes and is free of isocyanates and the composition without crosslinking agent
Realize one pack system and bicomponent system
There is high adhesive strength in a short time
Realize shape memory function.
Embodiment
Monomer 1:
Diethyl methylene malonate
Monomer 2:
Methyl-hexyl methylene malonate
Monomer 3:
Monomer 4:
Embodiment 1:(compares)
Aqueous polyurethane dispersion is prepared according to the embodiment 1 in WO 2006/087317, and is adjusted to solid content and is
50%.
Embodiment 2:
13.6g is placed in PE bottles of 100ml from the dispersion of embodiment 1 and is diluted with 3.4g deionized water.In room temperature
Under, it is vigorously stirred lower 3 solution of dropwise addition 3.4g monomer (20% w/w is in monomer 1).After stirring 12 hours, reaction is completed,
Reach 48% solid content.
Embodiment 3:
13.6g is placed in PE bottles of 100ml from the dispersion of embodiment 1 and is diluted with 3.4g deionized water.In room temperature
Under, it is vigorously stirred lower 4 solution of dropwise addition 3.4g monomer (20% solution is in monomer 1).After stirring 12 hours, reaction is completed, and is reached
47% solid content.
Embodiment 4:
6g is placed in PE bottles of 100ml from the dispersion of embodiment 1 and is diluted with 3g deionized water.At room temperature, acute
3 solution of 3g monomer is added dropwise under strong stirring (20% solution is in monomer 1).After stirring 12 hours, reaction is completed, and is reached 47% and is consolidated
Body content.
Embodiment 5:
13.6g is placed in PE bottles of 100ml from the dispersion of embodiment 1 and is diluted with 5.1g deionized water.In room temperature
Under, it is vigorously stirred lower 3 solution of dropwise addition 5.1g monomer (20% solution is in monomer 1).After stirring 12 hours, reaction is completed, and is reached
48% solid content.
Performance test:
Unless otherwise stated, carrying out PSA test according to AFERA test method 5012 and 5001.
Coating weight shown in table 1 is used to be coated to as carrier pressure-sensitive adhesive dispersionRN
It is 5 minutes dry at 90 DEG C on 36 (PET) films.The carrier coated with PSA is cut, the test-strips of 25mm wide are obtained.
A) shear strength
In order to measure shear strength, test-strips are adhered on steel plate with the overlapping of 12.5 × 12.5mm, with 1kg weight
Roller rolling is primary, then with the suspension of 1kg weight.Shear strength (cohesive force) is at (23 DEG C of standard conditions；50% relative humidity) under
Measurement.The measurement of shear strength is that weight falls the required time；In each case, by 5 survey calculation average values.
B) peel strength
In order to measure peel strength, test-strips are adhered on steel plate.At (23 DEG C of standard conditions；50% relative humidity)
Under, by the way that test-strips are separated by 180 ° of angle by the speed of 300mm/min from steel plate and measure the power in terms of N/25mm
To measure peel strength (adhesion strength).
Pressure-sensitive adhesive film is prepared with the polymeric dispersions from embodiment 1,2,3 and 5.
Table 1 summarizes the condition and result of PSA test.
Table 1: test result
Test condition:
Carrier:RN 36 (polyethylene terephthalate (PET) Biaxially oriented film)
Liner: siliconised paper (43gelb)
Width: 25mm
5min at 90 DEG C dry
Test speed: 300mm/min
Climatic chamber: 23 DEG C, 50% relative humidity
Shear strength: steel plate, be overlapped 12.5 × 12.5mm, time of contact 10 minutes, weight 1kg
Temperature: room temperature
It is clear that impurity shows high cohesive force and high adhesion to steel as water-borne pressure sensitive adhesive stick
Power.
Embodiment 6:
The polyurethane of embodiment 1 is diluted to 10% solid content with ethyl alcohol.The solution is rubbed (stainless in two samples
Steel) on and it is dry.By 60% monomer 1,20% monomer 2,20% thickener Vinnol H15/45M (Wacker) 0.2g it is mixed
It closes object and is placed in 625mm2It is between the sample of overlapping region and fixed.At room temperature after 48h, lap shear test (Zwick is carried out
Roell testing machine, 10mm/min).
Reach the shear strength of 6MPa.
Embodiment 6A (comparison)
Experiment 6 uses solution of 1% sodium benzoate in ethyl alcohol to carry out as raw material instead of PU.
It was found that shear strength is only 2MPa.
Embodiment 7:
Aqueous polyurethane dispersion is prepared according to the embodiment 1 in DE 2645779, and is adjusted to 39% solid content.
Embodiment 8:
The dispersion brushing of embodiment 7 is on stainless steel and dry, obtain not mucous membrane (0.1g/625mm2).It will be single
3 solution of body (20% w/w is in monomer 1) in very thin film (< 0.01g) erasing to one block of plate, and by the plate with
Second piece (being free of monomer) forces together, and is overlapped 625mm2And it is fixed.At room temperature after 48h, lap shear test is carried out
(Zwick Roell testing machine, 10mm/min).
Reach the shear strength of 8.8MPa.
Other lap shear samples are placed two weeks in air in 120 DEG C of baking oven.It is adjusted again after two weeks at 120 DEG C
Section finds that shear strength is still 5.8MPa to room temperature.
Embodiment 9:
The dispersion brushing of embodiment 7 is on stainless steel and dry, obtain not mucous membrane (0.1g/625mm2).It will be single
4 solution of body (20% w/w is in monomer 1) in very thin film (< 0.01g) erasing to one block of plate, and by the plate with
Second piece (being free of monomer) forces together, and is overlapped 625mm2And it is fixed.At room temperature after 48h, lap shear test is carried out
(Zwick Roell testing machine, 10mm/min).
Reach the shear strength of 8MPa.
Embodiment 10 (comparison)
The dispersion brushing of embodiment 7 is on stainless steel and dry, obtain not mucous membrane (0.1g/625mm2).By two
Block plate is with 625mm2Overlapping force together and fix.At room temperature after 48h, lap shear test (Zwick Roell examination is carried out
Test machine, 10mm/min).
Reach the shear strength of only 2MPa.
Claims (17)
1. polyurethane-vinyl hybrid polymer object, by least one anion polyurethane and at least one polymerizable vinyl
It closes object to be made, wherein polymerizable vinyl compound is selected from methylene malonate, methylene 'beta '-ketoester and methylene beta-diketon；
Wherein
A) the polyurethane-vinyl hybrid polymer object by first with aqueous anionic polyurethane dispersion coat substrate and with
It is applied and is formed outside with polymerizable vinyl compound afterwards, wherein the anionic group of polyurethane and polymerizable vinyl chemical combination
The ratio of the vinyl of object is greater than 1:9；
Or
B) wherein the polyurethane-vinyl hybrid polymer object is formed in aqueous dispersion.
2. polyurethane-vinyl hybrid polymer object according to claim 1, wherein the anionic group of the polyurethane with
The molar ratio of the vinyl of polymerizable vinyl compound is greater than 1:1.
3. polyurethane-vinyl hybrid polymer object according to claim 1 or 2, wherein the polyurethane has 50mmol/
The amount of the anionic group of kg to 500mmol/kg, anionic group is selected from carboxylate group, sulphur based on siccative, and wherein
Sulfonate groups and phosphate groups.
4. polyurethane-vinyl hybrid polymer object according to any one of claim 1 to 3, wherein the polyurethane has
There is the amount of the anionic group of 50mmol/kg to 500mmol/kg, anionic group is selected from carboxylic acid based on siccative, and wherein
Foundation group.
5. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the anion is poly-
Urethane is made of following
A) diisocyanate,
B) molal weight greater than 500 to 5000g/mol polyester-diol and/or molal weight be 240 to 5000g/mol it is poly-
Ether glycol,
C) with the glycol of carboxylic acid group, and
D) optionally other simple functions or polyfunctional compound are different from a)-c) and have selected from alcoholic extract hydroxyl group, primary amino group,
The reactive group of secondary amino group and isocyanate group.
6. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the anion is poly-
Glass transition temperature of the urethane before the polymerization of polymerizable vinyl compound is lower than 0 DEG C, preferably shorter than -10 DEG C.
7. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polymerizable second
Alkenyl compound is selected from formula R1- O-C (O)-C (C=CH2)-C(O)-O-R2Compound methylene malonate,
Or in which polymerizable vinyl compound is selected from formula R1- C (O)-C (C=CH2)-C(O)-O-R2Compound methylene
Base 'beta '-ketoester,
Or in which polymerizable vinyl compound is selected from formula R1- C (O)-C (C=CH2)-C(O)-R2Compound methylene
Beta-diketon,
Wherein R1、R2Be each independently C1-C15 alkyl, C2-C15 alkenyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base,
Halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or
Heteroaryl-(C1-C15 alkyl) or alkoxy-(C1-15 alkyl), each is optionally replaced by following group: C1-
C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-
C15 alkyl), it is aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl, nitro, folded
Nitrogen base, cyano, acyloxy, carboxyl, ester or sulfonyl；
Or in which R1And R25-7 circle heterocyclic ring is collectively formed in carbon atom in connection, and the heterocycle is optionally by following group
Replace: C1-C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle
Base-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl,
Nitro, azido, cyano, acyloxy, carboxyl, ester or sulfonyl.
8. polyurethane-vinyl hybrid polymer object according to any one of claim 1 to 6, wherein the polymerizable second
Alkenyl compound is selected from the compound of following formula:
Wherein R1、R2Be each independently C1-C15 alkyl, C2-C15 alkenyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base,
Halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or
Heteroaryl-(C1-C15 alkyl) or alkoxy-(C1-15 alkyl), each is optionally replaced by following group: C1-
C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle-(C1-
C15 alkyl), it is aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl, nitro, folded
Nitrogen base, cyano, acyloxy, carboxyl, ester or sulfonyl；
Or in which R1And R25-7 circle heterocyclic ring is collectively formed in carbon atom in connection, and the heterocycle is optionally by following group
Replace: C1-C15 alkyl, halogenated-(C1-C15 alkyl), C3-C6 naphthenic base, halogenated-(C3-C6 naphthenic base), heterocycle, heterocycle
Base-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio group, hydroxyl,
Nitro, azido, cyano, acyloxy, carboxyl, ester or sulfonyl；
[A]-representative-(CRARB)n-、
-(CRARB)n- O (C=O)-(CH2)1-15(C=O) O- (CRARB)n-、-(CH2)n-[CY]-(CH2)n, polybutadiene-base connect
Connect group, polyethylene glycol linking group, polyethers linking group, polyurethane linking group, epoxy linking group, polyacrylic acid connection
Group or polycarbonate linking group；
RAOr RBIt is each independently H, C1-C15Alkyl, C2-C15The part that alkenyl, following formula indicate:
Wherein L is linking group selected from the following: alkylidene, alkenylene, halogeno alkylen, cycloalkylidene, cycloalkylidene, Asia are miscellaneous
Ring group, heterocycloalkylene, aryl-alkylidene, inferior heteroaryl or heteroaryl-(alkylidene) or alkoxy-(alkylidene), it
Respectively optionally for branching and respective optionally replaced by following group: alkyl, halogenated alkyl, naphthenic base, halogen
Substituted naphthene base, heterocycle, heterocycle-(alkyl), aryl, aryl-(alkyl), heteroaryl, C1-C15Alkoxy, C1-C15Alkane sulphur
Base, hydroxyl, nitro, azido, cyano, acyloxy, carboxyl, ester replace, each optionally branching；
R3Independently selected from above-mentioned R2Defined in group；
[CY] indicates alkyl, alkenyl, halogenated alkyl, naphthenic base, halogenated cycloalkyl, heterocycle, heterocycle-(alkyl), aryl-
(alkyl), heteroaryl or heteroaryl-(alkyl) or alkoxy-(alkyl)；
The integer that n is 1 to 25；
The integer that m is 1 to 25；
And Q respectively representative-O- or direct key.
9. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polymerizable second
Alkenyl compound is selected from formula R1- O-C (O)-C (C=CH2)-C(O)-O-R2Compound, wherein R1、R2It is each independently C1-
C10 alkyl；
Or in which polymerizable vinyl compound is selected from the compound of following formula
Wherein R1、R2It is each independently C1-C10 alkyl,
A is selected from C1-C10 alkylidene and-X-Ph-Y-, wherein X and Y C1-C10 alkylidene each independently.
10. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polyurethane-
Vinyl hybrid polymer object is included in water-borne dispersions.
11. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polyurethane-
Vinyl hybrid polymer object is at room temperature by hemicrystalline and be made of amorphous anion polyurethane；
Or wherein polyurethane-vinyl hybrid polymer object at room temperature be crystallization and by hypocrystalline anion polyurethane system
At.
12. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polymerizable second
Alkenyl compound is methylene malonate.
13. polyurethane-vinyl hybrid polymer object according to any one of the preceding claims, wherein the polyurethane
The ratio of the vinyl of anionic group and polymerizable vinyl compound is greater than 1:1, and wherein polymerizable vinyl chemical combination
Object is at least one methylene malonate with two or more methylene malonate groups.
14. the two-component composition of polyurethane-vinyl hybrid polymer object is used to form, wherein the first liquid composition includes extremely
A kind of few anion polyurethane, second liquid composition include at least one selected from methylene malonate, methylene 'beta '-ketoester
With the polymerizable vinyl compound of methylene beta-diketon.
15. the method for forming polyurethane-vinyl hybrid polymer object,
Wherein at least one anion polyurethane and at least one are selected from methylene malonate, methylene 'beta '-ketoester and methylene
The polymerizable vinyl compound of beta-diketon reacts,
It wherein reacts and carries out in liquid medium, to form the single group for containing at least one polyurethane-vinyl hybrid polymer object
Subassembly object；
Or wherein by the first liquid composition comprising at least one anion polyurethane and include at least one
The second liquid composition of polymerizable vinyl compound mixes, and is subsequently applied on substrate, and polyurethane-vinyl mixes
The formation of polymer at least partly occurs after being administered on substrate；
Or wherein polyurethane-vinyl hybrid polymer object by first at least one anion polyurethane coat substrate and with
Applied first coating at least one polymerizable vinyl compound afterwards outside and formed, wherein the anionic group of polyurethane with can gather
The molar ratio for closing the vinyl of vinyl compound is greater than 1:9, preferably greater than 1:1.
16. the purposes of polyurethane-vinyl hybrid polymer object is used as the adhesive in sqtructural adhesive, in pressure-sensitive adhesive
The adhesive, adhesive in laminated adhesive, the adhesive in contact adhesive, the adhesive in ink, viscous in paint
Adhesive in mixture, coating, the adhesive for fiber bonding, in adhesive or high cohesion adhesive tape for particle bonding
Adhesive.
17. the method for forming laminate, wherein
(1) at least one anion polyurethane coated polymer film；
(2) coated polymer film is stored at least 1 day；
(3) coated polymer film is applied outside at least one polymerizable vinyl compound, wherein the anion base of polyurethane
Group and the molar ratio of the vinyl of polymerizable vinyl compound are greater than 1:9, preferably greater than 1:1,
And wherein polymerizable vinyl compound is selected from methylene malonate, methylene 'beta '-ketoester and methylene beta-diketon；
And wherein polymerizable vinyl compound has at least two, preferably at least three to be selected from methylene malonate base
It rolls into a ball, the functional group of methylene 'beta '-ketoester group and methylene beta-diketon group；With
(4) polymer film by outer painting is laminated on substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16197869.7 | 2016-11-09 | ||
| EP16197869 | 2016-11-09 | ||
| PCT/EP2017/077065 WO2018086860A1 (en) | 2016-11-09 | 2017-10-24 | Polyurethane-vinyl hybrid polymers, methods of making them and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109952330A true CN109952330A (en) | 2019-06-28 |
| CN109952330B CN109952330B (en) | 2021-07-02 |
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| CN201780069526.7A Expired - Fee Related CN109952330B (en) | 2016-11-09 | 2017-10-24 | Polyurethane-vinyl hybrid polymers, process for their preparation and their use |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US10894856B2 (en) |
| EP (1) | EP3538577A1 (en) |
| JP (1) | JP2019537527A (en) |
| CN (1) | CN109952330B (en) |
| WO (1) | WO2018086860A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115820169A (en) * | 2022-01-07 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Adhesive, adhesive tape, preparation method of adhesive tape and electrochemical device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| JP6267643B2 (en) | 2011-10-19 | 2018-01-24 | シラス・インコーポレイテッド | Polyfunctional monomer, method for producing polyfunctional monomer, polymerizable composition and product formed therefrom |
| US10607910B2 (en) | 2012-11-30 | 2020-03-31 | Sirrus, Inc. | Composite compositions for electronics applications |
| DE102019219214A1 (en) | 2018-12-17 | 2020-06-18 | Basf Se | Compositions comprising multifunctional vinyl compounds in mini-emulsion and their use as crosslinkers for polymers |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN109952330B (en) | 2021-07-02 |
| EP3538577A1 (en) | 2019-09-18 |
| US10894856B2 (en) | 2021-01-19 |
| US20190256639A1 (en) | 2019-08-22 |
| JP2019537527A (en) | 2019-12-26 |
| WO2018086860A1 (en) | 2018-05-17 |
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